2-carbomethoxy-1-methylvinyl ethyl phosphonothioates

ABSTRACT

NEW COMPOUNDS CORRESPONDING TO THE FORMULA   R-P(=X)(-R1)-O-C(-R2)=CH-COO-CH3   WHEREIN X CAN BE SULFUR OF OXYGEN; R CAN BE SELECTED FROM A GROUP CONSISTING OF ALKYL, HALOALKYL, ALKOXY, THIOALKYL AND ARYL; R1 CAN BE SELECTED FROM A GROUP CONSISTING OF THIOALKY, AMINOALKYL, THIOALKYLNITRILE, THIOALKYL ACETATE, THIOALKY ACETAMIDE, THIOALKYNYL, AMINE, THIOARYL, NITROARYL, HALOGENATED THIOARYL, THIOALKYLARYL, AMINO OXAZOLIDINE, KETO OXIME, AMINOARYL, AMINOCYCLOALKYL, AMINOALKYLARYL, AMINO FURFURYL, CYCLOALKYLAMINE ALKOXY, AND ALKENYLOXY; AND R2 CAN BE SELECTED FROM A GROUP CONSISTING O OR ARYL AND ALKYL,. THE COMPOSITIONS DESCRIBED HEREIN ARE USEFUL AS INSECTICIDES AND MITICIDES.

United States Patent C 3,784,589 Z-CARBOMETHOXY-l-METHYLVINYL ETHYL PHOSPHONOTHIOATES George B. Large, Pinole, Califi, assignor to Stautfer Chemical Company, New York, NY.

No Drawing. Filed Sept. 21, 1970, Ser. No. 74,136 Int. Cl. A01n 9/36; C07f 9/40 US. Cl. 260-941 9 Claims ABSTRACT OF THE DISCLOSURE New compounds corresponding to the formula Cor-C wherein X can be sulfur or oxygen; R can be selected from a group consisting of alkyl, haloalkyl, alkoxy, thioalkyl and aryl; R can be selected from a group consisting of thioalkyl, aminoalkyl, thioalkylnitrile, thioalkyl acetate, thioalkyl acetamide, thioalkynyl, amine, thioaryl, nitroaryl, halogenated thioaryl, thioalkylaryl, amino oxazolidine, keto oxime, aminoaryl, aminocycloalkyl, aminoalkylaryl, amino furfuryl, cycloalkylamine alkoxy, and alkenyloxy; and R can be selected from a group consisting or aryl and alkyl. The compositions described herein are useful as insecticides and miticides.

DESCRIPTION OF THE INVENTION The present invention is concerned with a novel group of compounds which can be generally described as vinyl phosphorus derivatives, and are used as pesticides, especially effective against mites and insects.

The compounds are represented by the general formula 0 Oz-CHa 'Method 1 This first method is a general procedure and can be applied to the synthesis of a greater variety of products falling within the scope of the above-noted general formula. Thus, compounds are synthesized by reacting a phosphoro dichloridate with a beta-keto ester in the presence of a solvent such as benzene, tetrahydrofuran and the like, and a base. The product formed by this reaction is then reacted with an appropriate nucleophilic ice reagent to form the end product. This latter reaction is carried out in the presence of a base. Compounds numbered 1 through 9 and 18 through 60 were synthesized by this procedure.

Method 2 This method is more specific and is limited to the phosphonodithio analogs encompassed by the general formula above-described. Thus, the compounds can be synthesized by reacting an alkyl thionophosphine sulfide with a betaketo ester in the presence of a solvent such as benzene, tetrahydrofuran and the like, and a base to form the appropriate salt of the 0-enol phosphonodithioic acid. This intermediate is not isolated and is reacted with a suitable halide to form the end product. Compounds numbered 10 through 17 were synthesized by this procedure.

In order to illustrate the merits of the present invention, the following examples are provided.

EXAMPLE 1 Preparation of 2-carbomethoxy-l-methylvinyl ethylphosphonothio chloridate To a stirring mixture of 178.3 parts 1.1 moles) of ethylphosphonothio dichloridate and 116.2 parts (1.0 moles) methyl acetoacetate in 1 liter of benzene at 10 was dripped a solution of 111.1 parts (1.1 moles) triethylamine in ml. benzene. A temperature of 10 C. was maintained during the addition of the base. The mixture was allowed to attain ambient temperature and then heated to 60 C. for four hours, cooled and washed with 300 ml. of dilute aqueous HCl and twice with 300 m1. ice Water, dried over anhydrous MgSO and volatiles removed on rotary evaporator. The product was distilled collecting that fraction which came oil at 93-96/0.12 mm. The yield was 149.9 parts or 62%.

EXAMPLE 2 Preparation of 2-carbomethoxy-l-methyl-vinyl-N- (2-propyl) ethylphosphonamidothionate lDissolve 6.05 parts (0.025 moles) of 2-carbomethoxyl-methylvinyl ethylphosphonothio chloridate and 3.54 parts isopropyl amine in 100 ml. benzene and stirred for two hours at room temperature. The product was washed with dilute aqueous HCl and water until neutral, dried over an hydrous Mg'SO and volatiles removed on rotary evaporator. The yield was 7.5 parts or 76%; 11 1.5080.

EXAMPLE 3 Preparation of O Z-carbomethoxyl-methylvinyl -S- ethyl-ethylphosphonodithioate To a stirring solution of 7.4 parts (0.03 mole) ethylthionophosphine sulfide dimer and 10 ml. triethylamine in ml. benzene was added 7.0 parts (0.06 mole) methyl acetoacetate. The mixture was stirred for 30 minutes. Then, 11.0 parts (0.07 mole) of ethyl iodide was added and warmed to 50 C. and stirred for 2 hours. The mixture was cooled and washed with 50 ml. of 5% NaHOO 50 ml. 10% aqueous HCl and Water until neutral, dried over anhydrous 'MgSO and volatiles removed on rotary evaporator. The yield was 13.0 parts of 81%; 11 1.5312.

Other compounds were prepared in an analogous manner starting with the appropriate starting materials, as outlined above. The following is a table of compounds representative of those embodied by the present invention. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

TABLE ICn tinued TABLE I Cpd. f No. R X R1 R: P o- H R G C a7 01H 8 CH:

OC=CH i ggf R X R! as 01H; s cm CH: 1 C2115 s S-CzH omoon:

s nnomcm): cm 39 S S SCHzCHa CH: NH-JJH S NHCH(CH3)2 CH3 1. HFCHPCH 0 4o 0211, s CHz-CH; 0H,

s NHCH CHM CH3 0 NHCHKJBZ): om NH H S SCHzCHa CH3 BIZ-CH3 S SCHzGH: CH: 41"" 02H s CH NHOH:

g g g gg; 42...... 0,11, s 0H, CH: S SCH CHI CH: s SCHZCEN CH1 i s CH8 H-CHa I s om o-oomom HPCH' CHs 43.... 02H: 8 CH: CHI I SCHzC-NHCH:

I t 1 L i 15...... C111; s 0H SCH: Cl

44 CzHa S OH; CH;

CH s SCHSCHCH CH3 gg: 2 ggjlgagg 8% NH JH CH2 omcmom): C N a s 02H: S g ofi 3 8% 45 C2115 B EH3 CHI 0 H S N a 3 oiHZ s mom): CH3 NH S NHCHZCH' 46 02H s NHwHm-om CH:

S 41 02m s cm 24 (31H; 8 S 01 CH3 48 0211, s nmonmom on; 49----.- C2H5 s NHomcmom CH; 60 02H 8 NH(CHz)CH 0H- 25-.---- CzHg; S SCHzCHzCHl 51 02H 8 CHI 26 c H s cm 2 NHCHzC H2)aCH;

27 02115 S NHmcHi): CH: 52 01H. 8 NH(GHz) 0Ha CH 3 02 5 8 CH; 28.. C2 s S O@ SCHZ a NHCHzCHz 54 02H 2 sn cm 2%: mm B 01 8 2%: s CH: CH: 5 fififiir fibca 8% Z 3 I 3 O 0 01 s 0CH(CHz)2 CH3 5 OCH2CH=CH2 CHa S N cm TESTING PROCEDURE J (1) House fly (Musca domestica (L.))

Hz-CH: H HCH CH CH CH (A) Film residue: A stock solution contalning 100 33 8& 2 g i f ,ugJml. oi the toxicant in an appropriate solvent is pre- 33 02H! S N=C(CHaa)I pared. Aliquots of this solution are combined with one ml. of an acetone-peanut oil solution in a dish, 55 mm. in CH CH 34 s a diameter, and allowed to dry. The aliquots are varied to ON: achieve desired toxicant concentrations ranging from 100 Ht zcHi g. per dish to that at which 50% mortality is obtained.

The dishes are placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with as 02H S C cloth netting. Twenty-five female house flies are introduced into the cage and the percent mortality is recorded after 48 hours. LD-SO values are expressed in terms of 36...... C211: S NHCH2CH=CH2 CH: 7 g 25 Q flies (II) German cockroach (Blattella germanica (Linn)) Ten one-month nymphs are placed into a circular cardboard cage sealed on one end with cellophane and covered by cloth netting on the other. Aliquots of the toxicant, dissolved in an appropriate solvent, are diluted in water to which has been added 0.0002% of a conventional Wetting agent such as polyoxy-ethylene sorbitan monolaurate ether of alkylated phenols blended with organic sulfonates. Test concentrations range from 0.1% to that at which 50% mortality is obtained. Each of these aqueous suspensions are sprayed onto the insects, through the cloth netting, by means of a hand spray gun. Percent mortality is recorded after 72 hours and the LD-SO values are expressed as percent of toxicant in the aqueous spray.

(HI) Lygus bug (Lygus hesperus (Knight)) Same as for the German cockroach (H) except that the test concentrations range from 0.05 to that at which 50% mortality is obtained.

(IV) Salt-marsh caterpillar (Estigmene acrea (Drury)) Test solutions are prepared in an identical manner and concentrations are the same as those for the German cockroach (II). Sections of bitter dock (Rumex obtusifolius) leaves, 1l.5 inches in length are immersed in the test solutions for -15 seconds and placed on a wire screen to dry. The dried leaf is placed on a moistened piece of filter paper in a petri dish and infested With five third-instar larvae. Mortality of the larvae is recorded after 72 hours and the LD-SO values are expressed as percent active ingredient in the aqueous suspensions.

(V) Beet armyworm (Spodoptera exigua (Hiibner)) Same as for salt marsh caterpillar except the leaves of Romaine lettuce (Latuca sativa) were used as the host plant.

(VI) Tobacco budworm (Heliothis virescens (F.))

Same as for salt marsh caterpillar except the leaves of Romaine lettuce (Latuca sativa) were used as the host plant.

6 (VII) Black bean aphid (Aphis fabae (Scop.))

Nasturtium (Tropaeolum sp.) plants, approximately 2-3 inches tall, are transplanted into sandy loam soil in 3 inch clay pots and infested with -75 aphids of mixed ages. Twenty-four hours later they are sprayed, to the point of runoff, with aqueous suspensions of the toxicant. The suspensions are prepared as in previously described tests (II, III, IV and V). Test concentrations ranged from 0.05% to that at which 50% mortality is obtained. Mortality is recorded after 48 hours and the LD-50 values are expressed as percent active ingredient in the aqueous suspensions.

(VIII Two-spotted mite (Tetranychus urticae (Koch)) Same as for the black bean aphid (VII) except that pinto beans (Phaseolus sp.) are utilized as the host plant rather than nasturtiums.

(IX) Systemic tests (A) Black bean aphid: Aliquots of the toxicant dissolved in an appropriate solvent are incorporated into 1 pound samples of sandy loam soil and placed into 1 pint ice-cream cartons. Test concentrations range from 10 p.p.m. of toxicant per pound of soil down to that at which 50% mortality is obtained. Nasturtium (Tropaeolum sp.) plants approximately 2-3 inches tall are transplanted into the treated soil and infested with 50-75 aphids of various ages. Mortality is recorded 72 hours after infestation, and LD-50 values are expressed as p.p.m. of active ingredient per pound of soil.

(B) Two-spotted mite: Aliquots of the toxicant dissolved in an appropriate solvent are diluted in water and placed in glass bottles. Concentrations of active ingredient range from 10 p.p.m. to that at which 50% mortality is obtained. Pinto bean (Phaseolus sp.) plants with expanded primary leaves are placed in the solution so that the roots and major portions of the stern are completely immersed. Immediately after, the leaves are infested with 7 5-100 mites of various ages. Mortality of adults, nymphs and eggs is recorded after one week, and LD-50 values are expressed as p.p.m. of toxicant in the aqueous suspensions.

The results of the above tests are set forth in the following table.

TABLE II.-LD VALUES Compound LB,

Two-spotted mites BAS,

SMC, TBW, BAW, PE, Eggs, SYS, u ber g./25 9 percent percent percent percent percent percent percent percent percent percent TABLE II-Continued Two-spotted mites Compound HF, GR, LB, BA, BAS, sMo, TBW, BAW, PE, Eggs, SYS, number gt/255? percent percent percent percent percent percent percent percent percent percent .03 .001 .0003 3 .01 .1 .05 .03 .05 .8 .003 001 .0003 s .1 03 .05 .03 .05 3 .01 001 .0003 .05 .05 .05 .01 .03 s .1 03 .0003 .1 .3 .1 .03 .03 10 .003 003 .0003 3 .01 .1 .05 .03 .03 10 .1 03 .03 10 .1 .1 .1 .05 .05 .01 003 .003 10 .1 .1 .1 .05 .05 10 .1 0003 .003 .1 .1 .1 .05 .05 .1 03 .005 10 .1 .1 .05 .05 .03 10 01 0003 0003 1 1 0s 03 03 05 10 .003 0003 .0003 .5 .05 .01 .002 003 .03 3 .005 0003 .0003 .s .03 .003 .005 .03 .05 3 008 005 0005 10 1 05 03 05 05 10 .1 .05 003 .1 .1 .1 .1 .05 .05 .1 .03 00s 10 .1 .1 .1 .03 .05 10 .05 .03 001 10 .1 .1 .1 .03 .03 10 01 003 001 3 0. 1 005 003 05 05 1 .03 003 003 10 .05 .05 .03 05 .05

What is claimed is: 6. A compound as set forth in claim 1 wherein R is 1. Compounds corresponding to the formula O-(2-propanone oximino).

X R 7. A compound as set forth in claim 1 wherein R is O-(3-methyl-2-butanone oximino). 8. A compound as set forth in claim 1 wherein R is O-C: H isopropylthio.

5 9. A compound as set forth in claim 1 wherein R is butylthio. wherein X is sulfur; R is ethyl; R can be selected from R f e Ci 3. group consisting of thioalkyl having 1 to 4 carbon atoms, thiopropynyl, and keto oxime having from 3 to 5 UNITED STATES PATENTS carbon atoms; and R is methyl. 3,035,079 5/ 1962 Berlgel -9 2. A compound as set forth in claim 1 wherein R is 3,053,729 9/1962 S1111 260-941 UX methylthio. 3,450,801 6/1969 Dawson et a1. 260-941 3. A com ound as set forth in claim 1 wherein R is ethylthm p 1 ANTON H. SUTTO, Primary Examiner 4. A compound as set forth in claim 1 wherein R is propynylthiol US. Cl. X.R.

5. A compound as set forth in claim 1 wherein R is 260307 F, 326.61, 347.2, 940, 942, 943; 424-200, propylthio. 203, 210, 211, 212 

